Denatured materials



STATES PATENT OFFICE DENATURED MATERIALS Hamline M. Kvalnes, Wilmington, DeL, assignor to E. I. du Pont de Nemours & Company, Wilmington, Del.,'a corporation of Delaware No Drawing. Application November 9, 1937, Serial No. 173,704

6 Claims. (01. 20277) This invention relates to denaturants and It is an object of the present invention to more particularly to denatured materials such as overcome the disadvantages of the prior art alcohols and esters and the method of denaturing and to provide a new denaturant and a denathem. tured material which possess unusual character- Many proposals have been made in the past istics previously desired but up until now unob- 5 for the use of various substances which, when tained. mixed with a substance such as an alcohol, an It is a further object of the present invention ester or the like, completely change its taste to provide a denatured ethyl alcohol which posand odor so that it cannot be diverted from its sesses a distinctive but unobjectionable odor, and

10 intended use. For example, this procedure has a taste which makes the ethyl alcohol unpotable, 0 been applied to methanol to avoid its being taken he e taste the d being vinternally, as well as to ethanol and other alb from the thy a coho cohols which might otherwise be diverted from It s n additional ject of this inven ion their intended commercial use to that f a, bevto provide denatured esters of such a character erage. Similarly, materials such as ethylacethat I if converted to alcohols the denaturant 15 tate, and other esters, which might fairly easily causes such alcohols to be unp and O a be otherwise converted to alcohols and thus didistinctive d t e Obj ct of t is invenverted from their intended use, have likewise tien iS t e production o a de t d so e. been denatured. Upon chemical treatment of a gasoline which y be readily identified 2,0 such esters, the denaturant has been intended to due to its d a u ant content. carry over to the alcohol and cause it to be unh r bj ts and adva ta s f t e pr s nt potable. invention will be apparent by reference to the Materials which have been proposed as d following specification in which the preferred naturants before have had one or more characembodiments nd deta ls are Set forth.

teristics which adapt them for denaturing pur- According to t e Diesent invention a ur d 25 poses. There are, however, several specific feaal from which it is extremely difficult if tures which it is desirable to have in a denanot p s ib e to remove the denaturant is turant and all of which have not been possessed P p d y miXihg W th a ga o i e or an ester to a sufficient degree by many of the denaturants Such as ethyl acetate an o S ch s previously suggested. Thus, for example, it is methyl, y p py d the like, t v y 30 desirable that a denaturant have an obnoxious Small quantities of a tertiary alcohol Co tai taste and a distinctive odor. Substances have s o t elements a n, ydr en, and been proposed previously which possess disagree- Oxygen, boiling n e range of rom IOU-200 able tastes but the odor carried by the denaturu and haVihg e n l f mu a 3.; ant has often been of such a character as to make the complete denatured alcohol commercially undesirable.

Another characteristic which a denaturant R1 must possess is that of difficulty of removal from in which R1, R2 and R3 may be saturated or un- 40 the denatured medium. As rapidly as denatursaturated acyclic or isocyclic hydrocarbon groups. 40

ants have been proposed, methods have been dis- The denaturants of this invention are genercovered for their removal from the denatured ally applicable for treatment of any normally medium. The methods utilized for removal of liquid material which it is desired to denature, denaturants have been usually chemical treatalthough, preferably, the material to be denament of the denatured medium combined with or tured should have a boiling point, in the range 45 followed by various distillation steps and furof 30 C. to 250 C. From a material having a ther chemical treatment until, finally, relativeboiling point in this range it will be found exly pure alcohol has been obtained. Up to the tremely diflicult, if not impossible, to remove present invention very few, if any, denaturants my denaturant.

extremely difficult of removal have been pro- A wide range of alcohols may be successfully 50 posed which possess an unobjectionable but at denatured or distinguished from one another ac the same time distinctive odor together with such cording to this invention including, such, for a disagreeable taste that the combination pracexample, as methyl alcohol, ethyl alcohol, butyl tically prohibits the denatured medium from alcohol, isobutyl alcohol, isopropyl alcohol, and

being taken internally. others. In like manner, the denaturants of my 55 this invention may be applied to other esters such as methyl, propyl, isopropyl, butyl and isobutyl acetates and the like, or similarly to like formates, propionates, butyrates, isobutyrates and like esters. It will be found that alcohols produced from esters containing denaturing quantities of one or more denaturants of this invention are likewise denatured, being unpotable and possessing a distinctive odor.

Among the tertiary alcohols which are operable according to the present invention are:

1. 2-methyl-butanol-2 CH3) 2C( OH) .CzHs 2. 2-methyl-3-pentenol-2 CH3.CH:CH.C(CH3)2.OH 3-methyl-1-pentynol-3 CH3.CH2.C(CH3) (OH) .CECH 2,4-dimethyl pentanol 2 (CI-I3) 2C(OH) .CI-Iz.CH(CHa 2 2-methyl-5-hexenol-2 CH2 I CH.CH2.CH2.C( CH3) 20H 2-methyl-3-hexynol-2 (CH3) 2C(OH) .CC.C2H5 '7. 2-methyl-heptanol-2 (CH3) 2C (OH) .CH2.(CH2) 3.CH3 8. 4-propyl-1,6-heptadienol-4 (CH2: CH.CH2) 2C(OH) .(CI-lz) 2.CH3

The use of these alcohols is illustrated in the examples which follow in which, however, additional tertiary alcohol denaturants of this invention are described as the denaturing mediums.

These tertiary alcohols possess an etherealcamphoraceous odor and are unpotable because of taste. Both the odor and the taste persist in spite of the most drastic treatment utilized for their removal. So far as applicant is aware, there is no method by which these materials may be satisfactorily removed from the material denatured by them.

The following examples illustrate proportions of various materials which may be utilized as denaturants. It will be noted that small quantities only of the denaturant are necessary for denaturing purposes and that the material remaining after treatment for denaturant removal possesses a taste which renders the material unpotable and has a distinctive odor.

Example 1 An unpotable denatured alcohol was prepared by adding 1 volume of methyldiethyl carbinol to 100 volumes of pure ethyl alcohol.

Example 2 200 cc. of a denatured alcohol, prepared by adding 1 volume of dimethylpropyl carbinol to volumes of pure 95% ethyl alcohol, were mixed with 500 cc. of saturated salt solution, 500 cc. of water and 50 cc. of heavy petroleum oil. The mixture was shaken and allowed to camps-co stand approximately 2 hours. The alcoholic brine tion with other Example 3 A denatured alcohol, prepared by adding 1 volume of triethyl carbinol to 100 volumes of pure 95% ethyl alcohol, was treated by the procedure of Example 2. The distillate had, the odor and taste of the denaturant and was unpotable.

Example 4 100 cc. of denatured alcohol, prepared by adding 5 volumes of methyl isobutyl ethynyl carbinol to 100 volumes of pure 95% ethyl alcohol;

was mixed with 300 cc. of saturated salt solution, 100 cc. of water and 25 cc. of mineral oil. The mixture was shaken for 3 minutes and allowed to stand overnight. The water layer was shaken for 3 minutes with a second portion (20 cc.) of mineral oil and allowed to stand 1 hour. The alcoholic brine layer from the second extraction was shaken with 5 g. of activated carbon for 30 minutes and filtered. The filtrate was then given a similar treatment with a second 5 g. portion of activated carbon. The filtrate from the second carbon treatment was then distilled at a reflux ratio of 10:1 and a. draw-off rate of 1 cc. per minute using a fractionating column of approximately 15 theoretical plates. The distillate had the odor and taste of the denaturant and was unpotable.

Example 5 An unpotable denatured alcohol was prepared by adding 5 volumes of diisopropyl ethynyl carbinol to 100 volumes of pure 95% ethyl alcohol.

Example 6 Example 7 A denatured ethyl propionate was prepared by adding 2 volumes of dimethyl isobutyl carbinol to 100 volumes of pure ethyl propionate.

Example 8 A denatured ethyl acetate was prepared by adding 2 volumes of dimethyl ethynyl carbinol to 100 volumes of 95% ethyl acetate.

Example 9 A denatured gasoline was prepared by adding 3 volumes of methyl is'obutyl ethynyl carbinol to 100 volumes of gasoline.

Although not indicated in the examples above given, the materials of the present invention may be admixed with other denaturing materials, such, for example, as sulfur-containing materials, wood oil products, and other known denaturing materials. It may be desirable from time to time to add other denaturing materials which possess stronger and more disagreeable odors than the denaturants of the present invention as a method of distinguishing the denatured liquids or for other reasons. The materials of the present invention are miscible however, generally speaking, with anything with which ethyl alcohol is miscible and may, therefore, be utilized in conjuncdenaturing materials generally,

such as illustrated by the following additional examples which show representative, preferred mixtures.

Example 10 A completely denatured alcohol was prepared by mixing 100 parts of pure 95% ethyl alcohol, 3

- parts of the mixture of primary and secondary Example 11 A completely denatured alcohol was prepared by mixing 100 parts of pure 95% ethyl alcohol, 3 parts dimethyl ethylnyl carbinol, 4 parts of the mixture of pyroligneous bodies, free from methanol, produced by the destructive distillation of wood, and 1 part of gasoline. The resulting denatured alcohol possessed a distinctive odor and an unpotable taste.

Example 12 A denatured alcohol prepared by mixing 100 parts of pure 95% ethyl alcohol, 2 parts of methyl isobutyl ethynyl carbinol, 2 parts ofmethyl isobutyl ketone, 1 part of the sulfur-containing residues obtained in the refining of petroleum, known under the name of Agdite, and 1 part of gasoline. The denatured alcohol produced possessed a distinctive odor and a disagreeable taste which rendered the alcohol unpotable.

The proportions utilized according to the present invention may vary from a very small quantity, such as one-tenth of one per cent, up to ten per cent by volume or more of the alcohol, or ester which is to be denatured, the amount of denaturant depending entirely upon the degree of odor and taste desired. Small quantities are, however, generally suflicient, i. e., in the range of 0.1 to 5% by volume. A great advantage of the present denaturant resides in the fact that it does not render the alcohol, ester, gasoline or the like commercially and scientifically undesirable inasmuch as the general character of the denatured material is not changed by the incorporation of my denaturant.

Various changes may be made in the present invention without departing therefrom or sacrificing any of the advantages thereof.

I claim:

1. A denatured alcohol containing denaturing quantities of an unsaturated tertiary alcohol containing only carbon,.hydrogen, and oxygen, and boiling in the range of from 100 to 200 C.

2. A denatured alcohol containing 0.1-% by volume of an unsaturated tertiary alcohol containing only carbon, hydrogen, and oxygen, and boiling in the range of from 100 to 200 C.

3. A denatured ethyl alcohol containing 0.1- 10% by volume of an unsaturated tertiary alcohol containing only carbon, hydrogen, and oxygen, and boiling in the range of from 100 to 200 C.

4. A denatured ethyl alcohol containing 0.1- 5% by volume of an unsaturated tertiary alcohol containing only carbon, hydrogen, and oxygen, and boiling in the range of from 100 to 200 C.

5. A denatured alcohol containing denaturing quantities of dimethyl ethynyl carbinol.

6. A denatured alcohol containing denaturing quantities of methyl isobutyl ethynyl carbinol.

HAMLINE M. xvamas. 

